Optical element having antireflection film

ABSTRACT

The present invention provides an optical member having a plastic substrate and a multilayered antireflection film formed by vapor deposition, wherein at least one layer in the antireflection film is a hybrid layer formed of at least one inorganic substance selected from silicon dioxide, aluminum oxide, titanium oxide, zirconium oxide, tantalum oxide, yttrium oxide, and niobium oxide and an organosilicon compound that is a liquid at normal temperature and at atmospheric pressure and/or an organic compound not containing silicon that is a liquid at normal temperature and at atmospheric pressure as vapor deposition raw materials.

DESCRIPTION OF THE INVENTION

[0001] The present application claims priority under 35 U.S.C. § 119 ofJapanese Application No. 2002-378192, filed Dec. 26, 2002, thedisclosure of which is expressly incorporated by reference herein in itsentirety.

FIELD OF THE INVENTION

[0002] The present invention relates to an optical member having anantireflection film, and particularly to an optical member having anantireflection film with good productivity, which not only has anantireflection film having excellent properties such as low reflectanceand high transmittance but also has excellent impact resistance,adhesiveness, heat resistance, abrasion resistance and alkali resistanceon the plastic substrate.

BACKGROUND OF THE INVENTION

[0003] Hitherto, optical members in which an antireflection film havingan inorganic substance vapor deposited thereon is provided on a plasticsubstrate are known. Such optical members have excellent antireflectionproperties and resistance to scuffing.

[0004] However, these optical members having an antireflection film arenot sufficient in impact resistance and heat resistance. It is known toprovide a primer layer made of an organic substrate between a plasticsubstrate and an antireflection film. Also, in plastic lenses, therefractive index of a lens material becomes high, and plastic lensmaterials having an antireflection film and having a refractive index of1.70 or more, which are provided with a primer layer by dipping andvapor deposited with an inorganic substance, are proposed in the market(see EP 0964019 A1 (Patent Document 1)).

[0005] However, since the primer layer disclosed in Patent Document 1and the like is provided by coating a primer liquid on a plasticsubstrate, heating the primer solution for curing, and then vapordepositing an antireflection film thereon, there was some possibilitythat the film thickness of the primer layer does not become uniform.Also, with respect to the primer layer disclosed in Patent Document 1,since the primer layer is provided in atmosphere, whereas theantireflection film is provided in vacuo, there were involved problemssuch that foreign matters were liable to enter between theantireflection film and the primer layer and that it took a long periodof time to prepare final products.

[0006] Also, the optical member comprising a plastic lens materialhaving a refractive index of 1.70 or more as a substrate and having theforegoing primer layer and the antireflection film made of an inorganicvapor deposited substance provided thereon on a basis of this substratehad a problem in resistance to scuffing on the surface.

SUMMARY OF THE INVENTION

[0007] The invention provides an optical member having an antireflectionfilm with good productivity, which not only has an antireflection filmhaving excellent properties such as low reflectance and hightransmittance but also has excellent impact resistance, adhesiveness,heat resistance, abrasion resistance and alkali resistance on theplastic substrate.

[0008] It has been found that by providing a hybrid layer comprising aninorganic substance and an organic substance in at least one layer ofconstitutional layers of an antireflection film, an optical memberhaving an antireflection film, which has excellent abrasion resistance,impact resistance, adhesiveness, heat resistance and alkali resistance,is obtained.

[0009] The present invention relates to an optical member having aplastic substrate and a multilayered antireflection film formed by vapordeposition, characterized in that at least one layer in theantireflection film is a hybrid layer formed of at least one inorganicsubstance selected from silicon dioxide, aluminum oxide, titanium oxide,zirconium oxide, tantalum oxide, yttrium oxide, and niobium oxide and anorganosilicon compound that is a liquid at normal temperature and atatmospheric pressure and/or an organic compound not containing siliconthat is a liquid at normal temperature and at atmospheric pressure asvapor deposition raw materials. By normal temperature, we mean roomtemperature of about 25° C.

BRIEF DESCRIPTION OF THE DRAWINGS

[0010]FIG. 1 is a schematic view of a film forming device used in theinvention. The reference numbers in FIG. 1 have the following meanings

[0011]1: Optical type film thickness monitor

[0012]2: Substrate

[0013]3: Dome for holding substrate

[0014]4: Inlet A of organic substance

[0015]5: Inlet B of organic substance

[0016]6: Evaporation source

[0017]7: RF type ion gun

[0018]8: Inlet of ionized gas

[0019]9: Connection portion to exhaust system

[0020]10: Connection portion to external monomer heating (vaporizing)device

DETAILED DESCRIPTION OF THE INVENTION

[0021] The particulars shown herein are by way of example and forpurposes of illustrative discussion of the various embodiments of thepresent invention only. In this regard, no attempt is made to showdetails of the invention in more detail than is necessary for afundamental understanding of the invention, the description makingapparent to those skilled in the art how the several forms of theinvention may be embodied in practice.

[0022] The antireflection film of the invention is formed by vapordeposition. Also, for the sake of obtaining good film strength andadhesiveness, it is preferable that the antireflection film is formed byion beam assisted deposition. Other film constitutional layers of theantireflection film than the hybrid layer are not particularly limited.However, in order to obtain good physical properties such as anantireflection effect, it is preferable to have an SiO₂ layer or a mixedlayer of SiO₂ and Al₂O₃ as a low refractive index layer and an Nb₂O₅layer or a TiO₂ layer as a high refractive index layer, respectively.

[0023] In the invention, the inorganic substance that is used in thehybrid layer is at least one member selected from silicon dioxide,aluminum oxide, titanium oxide, zirconium oxide, tantalum oxide, yttriumoxide, and niobium oxide. These inorganic substances may be used singlyor in admixture. In the case where a plural number of inorganicsubstances are used, they may be physically mixed or may be in the formof a composite oxide, specifically SiO₂—Al₂O₃, etc.

[0024] In the invention, as the organic substance that is used in thehybrid layer, an organosilicon compound that is in the state of a liquidat normal temperature and at atmospheric pressure and/or an organiccompound not containing silicon that is a liquid at normal temperatureand at atmospheric pressure is used from the viewpoints of control ofthe film thickness and control of vapor deposition rate.

[0025] As the organosilicon compound, ones having, for example, astructure represented by any one of the following general formulae(a)-(d) are preferable.

[0026] In the general formulae (a) to (d), m and n each independentlyrepresents an integer of 0 or more; X₁ to X₈ each independentlyrepresents hydrogen, a saturated or unsaturated hydrocarbon group havingfrom 1 to 6 carbon atoms, an —OR¹ group, a —CH₂OR² group, a —COOR³group, an —OCOR⁴ group, an —SR⁵ group, a —CH₂SR⁶ group, an —NR⁷ ₂ group,or a —CH₂NR⁸ ₂ group; and R¹ to R⁸ each represents hydrogen or asaturated or unsaturated hydrocarbon group having from 1 to 6 carbonatoms. X₁ to X₈ may be any arbitrary functional group as describedpreviously, and all of them may be the same functional group, or a partor all of them may be different from each other without any limitations.

[0027] Specific examples of the hydrocarbon group having from 1 to 6carbon atoms represented by R¹ to R⁸ include a methyl group, an ethylgroup, an n-propyl group, an isopropyl group, an n-butyl group, anisobutyl group, a pentyl group, a hexyl group, a vinyl group, an allylgroup, an ethynyl group, a phenyl group, a cyclohexyl group, a propynylgroup, and an isopropenyl group.

[0028] Specific examples of the compound represented by the generalformula (a) include trimethylsilanol, diethylsilane,dimethylethoxysilane, hydroxymethyltrimethylsilane,methoxytrimethylsilane, dimethoxydimethylsilane, methyltrimethoxysilane,mercaptomethyltrimethoxysilane, tetramethoxysilane,mercaptomethyltrimethylsilane, aminomethyltrimethylsilane,dimethyldimethylaminosilane, ethynyltrimethylsilane,diacetoxymethylsilane, allyldimethylsilane, trimethylvinylsilane,methoxydimethylvinylsilane, acetoxy-trimethylsilane,trimethoxyvinylsilane, diethylmethylsilane, ethyltrimethylsilane,ethoxytrimethylsilane, diethoxymethylsilane, ethyltrimethoxysilane,dimethylaminotrimethylsilane, bis(dimethylamino)methylsilane,phenylsilane, dimethyldivinylsilane, 2-propynyloxytrimethylsilane,dimethyl-ethoxyethynylsilane, diacetoxydimethylsilane,allyltrimethylsilane, allyloxytrimethylsilane,ethoxydimethylvinylsilane, isopropenoxytrimethylsilane,allylaminotrimethylsilane, trimethylpropylsilane,trimethylisopropylsilane, triethylsilane, diethyidimethylsilane,butyldimethylsilane, trimethylpropoxysilane, trimethylisopropoxysilane,triethylsilanol, diethoxydimethylsilane, propyltrimethoxysilane,diethylaminodimethylsilane, bis(ethylamino)dimethylsilane,bis(dimethylamino)dimethylsilane, tri(dimethylamino)silane,methylphenylsilane, methyltrivinylsilane, diacetoxymethylvinylsilane,methyltriacetoxysilane, alloxydimethylvinylsilane,diethylmethylvinylsilane, diethoxymethylvinylsilane,bis(dimethylamino)methylvinylsilane, butyidimethylhydroxymethylsilane,1-methylpropoxytrimethylsilane, isobutoxytrimethylsilane,butoxytrimethylsilane, butyltrimethoxysilane, methyltriethoxysilane,isopropylaminomethyltrimethylsilane, diethylaminotrimethylsilane,methyltri(dimethylamino)silane, dimethylphenylsilane, tetravinylsilane,triacetoxyvinylsilane, tetraacetoxysilane, ethyltriacetoxysilane,diallyidimethylsilane, 1,1-dimethylpropynyloxytrimethylsilane,diethoxydivinyl-silane, butyldimethylvinylsilane,dimethylisobutoxyvinylsilane, acetoxytriethylsilane,triethoxyvinylsilane, tetraethylsilane, dimethyldipropylsilane,diethoxydiethylsilane, dimethyldipropoxysilane, ethyltriethoxysilane,tetraethoxysilane, methylphenylvinylsilane, phenyltrimeth-ylsilane,dimethylhydroxymethylphenylsilane, phenoxytrimethylsilane,dimethoxymethylphenylsilane, phenyltrimethoxysilane,anilinotrimethylsilane, 1-cyclohexenyloxytrimethylsilane,cyclohexyloxytrimethylsilane, dimethyl-isopentyloxyvinylsilane,allyltriethoxysilane, tripropylsilane,butyldimethyl-3-hydroxypropylsilane, hexyloxytrimethylsilane,propyltriethoxysilane, hexyltrimethoxysilane, dimethylphenylvinylsilane,trimethylsilylbenzonate, di-methylethoxyphenylsilane,methyltriisopropenoxysilane, meth-oxytripropylsilane,dibutoxydimethylsilane, methyltripropoxysilane,bis(butylamino)dimethylsilane, divinylmethylphenylsilane,diacetoxymethylphenylsilane, diethylmethylphenylsilane,diethoxymethylphenylsilane, triisopropoxyvinylsilane,2-ethylhexyloxytrimethylsilane, pentyltriethoxysilane, diphenylsilane,phenyltrivinylsilane, triethylphenylsilane, phenyltriethoxysilane,tetraallyl-oxysilane, phenyltri(dimethylamino)silane,tetrapropoxysilane, tetraisopropoxysilane, diphenylmethylsilane,diallylmethylphenylsilane, dimethyldiphenylsilane,dimethoxydiphenylsilane, diphenylethoxymethylsilane, tripentyloxysilane,diphenyidivinylsilane, diacetoxydiphenylsilane, diethyidiphenylsilane,diethoxydiphenylsilane, bis(dimethyl-amino)diphenylsilane,tetrabutylsilane, tetrabutoxysilane, triphenylsilane,diallyidiphenylsilane, trihexylsilane, triphenoxyvinylsilane,1,1,3,3-tetramethyldisiloxane, pentamethyldisiloxane,hexamethyldisiloxane, 1,3-dimethoxytetramethyldisiloxane,1,3-diethynyl-1,1,3,3-tetramethyldisiloxane,1,3-divinyl-1,1,3,3-tetramethyldisiloxane,1,3-diethoxytetramethyidisiloxane, hexaethyldisiloxane, and1,3-dibutyl-1,1,3,3-tetramethyldisiloxane.

[0029] Examples of the compound of the general formula (b) includehexamethyldisilazane, 1,3-divinyl-1,1,3,3-tetramethyidisilazane, and1,1,3,3-tetramethyldisilazane.

[0030] Examples of the compound of the general formula (c) includehexamethylcyclotrisiloxane, 1,1,3,3,5,5-hexamethylcyclotrisilazane,hexaethylcyclotrisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, andoctamethylcyclotetrasiloxane.

[0031] Examples of the compound of the general formula (d) include1,1,3,3,5,5,7,7-octamethylcyclotetrasilazane.

[0032] The number average molecular weight of these organosiliconcompounds is generally from 48 to 320, and preferably from 48 to 249from the standpoints of control of the organic components in the hybridfilm and strength of the film itself.

[0033] Next, as the organic compound not containing silicon, whichconstitutes the hybrid layer, ones containing a reactive group in theside chain or terminal end thereof and containing carbon and hydrogen asessential components, or ones containing a double bond are preferable.Specifically, compounds represented by the general formulae (e)-(g) maybe used.

[0034] In the general formulae (e) and (f), R⁹ represents a hydrocarbongroup having from 1 to 10 carbon atoms, which may contain nitrogen oroxygen, and R¹⁰ represents a divalent hydrocarbon group having from 1 to7 carbon atoms, which may contain oxygen; and in the general formula(g), X₉ to X₁₂ each represents hydrogen, a hydrocarbon group having from1 to 10 carbon atoms, or an organic group having from 1 to 10 carbonatoms and containing carbon and hydrogen as essential components andfurther containing at least one of oxygen and nitrogen as an essentialcomponent.

[0035] Specific examples of the compound of the general formula (e)include methyl glycidyl ether, butyl glycidyl ether, 2-ethylhexylglycidyl ether, decyl glycidyl ether, stearyl glycidyl ether, allylglycidyl ether, phenyl glycidyl ether, p-sec-butylphenyl glycidyl ether,p-tert-butylphenyl glycidyl ether, 2-methyloctyl glycidyl ether,glycidol, and trimethylolpropane polyglycidyl ether. Specific examplesof the compound of the general formula (f) include neopentyl glycoldiglycidyl ether, glycerol diglycidyl ether, propylene glycol diglycidylether, tripropylene glycol diglycidyl ether, polypropylene glycoldiglycidyl ether, 1,6-hexanediol diglycidyl ether, ethylene glycoldiglycidyl ether, diethylene glycol diglycidyl ether, and polyethyleneglycol diglycidyl ether.

[0036] Specific examples of the compound of the general formula (g)include vinylpyrrolidone, vinylcarbazole, methyl methacrylate, ethylmethacrylate, benzyl methacrylate, n-butyl methacrylate, isobutylmethacrylate, dimethylaminoethyl methacrylate, methacrylic acid,glycidyl methacrylate, vinyl acetate, and styrene.

[0037] Also, the number average molecular weight of the compoundsrepresented by the foregoing general formulae (e) to (g) is generallyfrom 28 to 320, and preferably from 28 to 249 while taking into accountthe control of the organic components in the hybrid film and thestrength of the hybrid film.

[0038] In the invention, as the method of forming a film of theorganosilicon compound and/or the organic compound not containingsilicon (hereinafter sometimes referred to as “organic substance”), informing the hybrid layer, the inorganic substance and the organicsubstance may be subjected to vapor deposition simultaneously withseparate vapor deposition sources to form a film as shown in FIG. 1.

[0039] Also, it is preferable from the viewpoint of control of the vapordeposition rate that an external tank in which the organic substance isstored is heated and reduced in pressure to feed the organic substanceinto a chamber, and a film is formed by ion beam assisted depositionusing an oxygen gas and/or an argon gas.

[0040] Also, in the invention, the organic substance is a liquid atnormal temperature and at atmospheric pressure and can be subjected tovapor deposition by direct heating without necessity of use of asolvent.

[0041] As shown in FIG. 1, it is effective for improving the impactresistance and abrasion resistance to provide an inlet of the organicsubstance just above a vapor deposition source of the inorganicsubstance, and it is preferable to feed the organosilicon compound fromthe lower portion and the organic compound not containing silicon fromthe upper portion, respectively.

[0042] The heating temperature of the external tank varies depending onthe evaporating temperature of the organic substance but may be set upat, for example, from 30 to 200° C., and preferably from 50 to 150° C.from the standpoint of obtaining a proper vapor deposition rate.

[0043] In the invention, the content in the film of the organicsubstance of the hybrid layer is preferably from 0.02% by weight to 25%by weight while taking into account an especially good modifying effectof physical properties.

[0044] In the invention, with respect to the constitution of themultilayered antireflection film to be formed on the plastic substrate,the hybrid layer is used in at least one layer of the film constitution.

[0045] The hybrid layer can be formed in an arbitrary layer in themultilayered antireflection film. Also, the hybrid layer can be formedin a plural number of the layers. In order to obtain especiallyexcellent impact resistance, it is preferable that the hybrid layer isprovided in the position most close to the lens substrate and/or theposition most far from the lens substrate. Also, in order to obtainespecially excellent adhesiveness, it is preferable that the hybridlayer is formed by ion beam assisted deposition.

[0046] In the ion beam assisted deposition, with respect to an output,it is especially preferable from the viewpoint of obtaining goodreaction that an accelerating voltage is in the range of from 50 to 700V and that an accelerating current is in the range of from 30 to 250 mA.As ionized gases that are used in carrying out the ion beam assisteddeposition, argon (Ar) or a mixed gas of argon and oxygen is preferablyused from the standpoints of reactivity and oxidation prevention duringthe film formation.

[0047] Also, in the optical member of the invention, for the sake ofimproving the adhesiveness, a layer made of a metal having a catalyticaction in forming the hybrid layer, for example, at least one memberselected from nickel (Ni), silver (Ag), platinum (Pt), niobium (Nb), andtitanium (Ti), can be provided as an undercoat beneath theantireflection film. A particularly preferred undercoat is a metalliclayer made of niobium from the viewpoint that better impact resistancecan be imparted.

[0048] In the case where the foregoing metallic layer is used as theundercoat, the impact resistance of the optical member is in generalimproved.

[0049] Also, the film thickness of the undercoat is not particularlylimited but is preferably in the range of from 1 to 5 nm from theviewpoint of obtaining lenses having good impact resistance andtransmittance.

[0050] The material of the plastic substrate that is used in theinvention is not particularly limited. Examples include methylmethacrylate homopolymers, copolymers of methyl methacrylate and atleast one other monomer, diethylene glycol bisallyl carbonatehomopolymers, copolymers of diethylene glycol bisallyl carbonate and atleast one other monomer, sulfur-containing copolymers, halogencopolymers, polycarbonates, polystyrenes, polyvinyl chlorides,unsaturated polyesters, polyethylene terephthalate, polyurethanes,polythiourethanes, and a polymer formed by polymerizing a compoundcontaining an epithio group.

[0051] Examples of a compound containing an epithio group include chainorganic compounds such as bis(β-epithiopropylthio)methane,1,2-bis(β-epithiopropylthio)ethane, 1,3-bis(β-epithiopropylthio)propane,1,2-bis(β-epi-thiopropylthio)propane,1-(β-epithiopropylthio)-2-(β-epi-thiopropylthiomethyl)propane,1,4-bis(β-epithiopropylthio)butane, 1,3-bis(β-epithiopropylthio)butane,1-(β-epithiopropylthio)-3-(β-epithiopropylthiomethyl)-butane,1,5-bis(β-epithiopropylthio)pentane,1-(β-epithiopropylthio)-4-(β-epithiopropylthiomethyl)pentane,1,6-bis(β-epithiopropylthio)hexane,1-(β-epithiopropylthio)-5-(β-epithiopropylthiomethyl)hexane,1-(β-epithiopropylthio)-2-[(2-β-epithiopropylthioethyl)thio]ethane, and1-(β-epithiopropylthio)-2-[[2-(2-β-epithiopropylthioethyl)thioethyl]thio]ethane.

[0052] Also, there are enumerated branched organic compounds such astetrakis(β-epithiopropylthiomethyl)methane,1,1,1-tris(β-epithiopropylthiomethyl)propane,1,5-bis(β-epithiopropylthio)-2-(β-epithiopropylthiomethyl)-3-thiapentane,1,5-bis(β-epithiopropylthio)-2,4-bis(β-epithiopropylthiomethyl)-3-thiapentane,1-(β-epithiopropylthio)-2,2-bis(β-epithiopropylthiomethyl)-4-thiahexane,1,5,6-tris(β-epithiopropylthio)-4-(β-epithiopropylthiomethyl)-3-thiahexane,1,8-bis(β-epithiopropylthio)-4-(β-epithiopropylthiomethyl)-3,6-dithiaoctane,1,8-bis(β-epithiopropythio)-4,5-bis(β-epithiopropylthiomethyl)-3,6-dithiaoctane,1,8-bis(β-epithiopropylthio)-4,4-bis(β-epithiopropylthiomethyl)-3,6-dithiaoctane,1,8-bis(β-epithiopropylthio)-2,4,5-trs(β-epithiopropylthiomethyl)-3,6-dithiaoctane,1,8-bis(β-epithiopropylthio)-2,5-bis(β-epithiopropylthiomethyl)-3,6-dithiaoctane,1,9-bis(β-epithiopropylthio)-5-(β-epithiopropylthiomethyl)-5-[(2-β-epithiopropylthioethyl)thiomethyl]-3,7-dithia-nonane,1,10-bis(β-epithiopropylthio)-5,6-bis[(2-1-epithiopropylthioethyl)thio]-3,6,9-trithiadecane,1,11-bis(β-epithiopropylthio)-4,8-bis(β-epithiopropylthio-methyl)-3,6,9-trithiaundecane,1,11-bis(β-epithiopropylthio)-5,7-bis(β-epithiopropylthiomethyl)-3,6,9-trithiaundecane,1,11-bis(β-epithiopropylthio)-5,7-[(2-β-epithiopropylthioethyl)thiomethyl]-3,6,9-trithiaundecane,and1,11-bis(β-epithiopropylthio)-4,7-bis(β-epithiopropylthiomethyl)-3,6,9-trithiaundecane,and compounds resulting from substitution of at least one hydrogen inthe episulfide group in these compounds with a methyl group.

[0053] Further, there are enumerated cyclic aliphatic organic compoundssuch as 1,3- or 1,4-bis(β-epithiopropylthio)cyclohexane, 1,3- or1,4-bis(β-epithiopropylthiomethyl)cyclohexane,bis[4-(β-epithiopropylthio)cyclohexyl]methane,2,2-bis[4-(β-epithiopropylthio)cyclohexyl]propane,bis[4-(β-epithiopropylthio)cyclohexyl]sulfide,2,5-bis(β-epithiopropylthiomethyl)-1,4-dithiane, and2,5-bis(β-epithiopropylthioethylthiomethyl)-1,4-dithiane, and compoundsresulting from substitution of at least one hydrogen in the episulfidegroup in these compounds with a methyl group; and aromatic organiccompounds such as 1,3- or 1,4-bis(β-epithiopropylthio)benzene, 1,3- or1,4-bis(β-epithiopropylthiomethyl)benzene,bis[4-(β-epithiopropylthio)phen-yl]methane,2,2-bis[4-(β-epithiopropylthio)phenyl]propane,bis[4-(β-epithiopropylthio)phenyl]sulfide,bis[4-(β-epithiopropylthio)phenyl]sulfone, and4,4′-bis(β-epithiopropylthio)biphenyl, and compounds resulting fromsubstitution of at least one hydrogen in the episulfide group in thesecompounds with a methyl group.

[0054] The optical member of the invention may have a cured coating filmbetween the plastic substrate and the undercoating.

[0055] As the cured coating film, a composition comprising metal oxidecolloid particles and an organosilicon compound represented by thefollowing general formula (I) is generally used.

(R¹¹)_(a)(R¹²)_(b)Si(OR¹³)_(4−(a+b))   (I)

[0056] In the formula, R¹¹ and R¹² each independently represents anorganic group selected from an alkyl group having from 1 to 8 carbonatoms, an alkenyl group having from 2 to 8 carbon atoms, an aryl grouphaving from 6 to 8 carbon atoms, an acyl group having from 1 to 8 carbonatoms, a halogen group, a glycidoxy group, an epoxy group, an aminogroup, a phenyl group, a mercapto group, a methacryloxy group, and acyano group; R¹³ represents an organic group selected from an alkylgroup having from 1 to 8 carbon atoms, an acyl group having from 1 to 8carbon atoms, and a phenyl group having from 6 to 8 carbon atoms; and aand b each independently represents an integer of 0 or 1,

[0057] Examples of the metal oxide colloid particles include tungstenoxide (WO₃), zinc oxide (ZnO), silicon oxide (SiO₂), aluminum oxide(Al₂O₃), titanium oxide (TiO₂), zirconium oxide (ZrO₂), tin oxide(SnO₂), beryllium oxide (BeO), and antimony oxide (Sb₂O₅). These metaloxide colloid particles can be used singly or in admixture of two ormore thereof.

[0058] With respect to a coating liquid for preparing the cured coatingfilm, the liquid can be prepared by the conventionally known method. Ifdesired, curing catalysts and various organic solvents and surfactantsfor the purposes of improving wettability at the time of coating andimproving smoothness of the cured coating film can also be contained.Further, ultraviolet ray absorbers, antioxidants, photostabilizers, ageresistors, and the like can be added so far as physical properties ofthe coating composition and the cured coating film are not affected.

[0059] Curing of the coating composition is carried out by hot airdrying or active energy ray irradiation, and with respect to the curingcondition, the curing is suitably carried out in hot air preferably atfrom 70 to 200° C., and particularly preferably at from 90 to 150° C.Incidentally, examples of the active energy rays include far infraredrays, and damages by heat can be suppressed to a low level.

[0060] Also, as the method of forming the cured film comprising acoating composition on the substrate, there is enumerated a method ofcoating the coating composition on the substrate. As the coatingmeasure, usually employed methods such as dipping, spin coating, andspraying can be applied. Of these measures, dipping and spin coating areespecially preferable from the standpoint of profile irregularity.

[0061] Also, for the sake of ensuring adhesiveness between the plasticsubstrate and the undercoating or designing to unify the initial filmforming state of the vapor deposition substance, the surface of thecured coating film may be subjected to treatment with an ionized gas. Asthe ionized gas in the pre-treatment by an ion gun, oxygen, argon (Ar),etc. can be used. With respect to an output, it is especially preferablefrom the viewpoint of obtaining good adhesiveness and abrasionresistance that an accelerating voltage is in the range of from 50 to700 V and that an accelerating current is in the range of from 50 to 250mA.

[0062] In the invention, it is possible to provide a primer layer madeof an organic compound between the plastic substrate and theantireflection film as described in the above cited Patent Document 1.For the sake of further improving the impact resistance, a primer layermade of an organic compound as the raw material may be provided betweenthe plastic substrate and the antireflection film, or between theplastic substrate and the cured coating film.

[0063] Examples of the primer layer include ones of forming a urethanebased film made of a polyisocyanate and a polyol as raw materials.Examples of polyisocyanates include adducts resulting from bondingseveral molecules of hexamethylene diisocyanate, 4,4′-cyclohexylmethanediisocyanate, and hydrogenated xylylene diisocyanate by various methodsand ones resulting from blocking isocyanurate, allophanate, biuret, orcarbodiimide with acetoacetic acid, malonic acid, methyl ethyl ketoxime,etc. On the other hand, examples of polyols include polyesters,polyethers, polycaprolactones, polycarbonates, and polyacrylates eachhaving a plural number of hydroxyl groups in one molecule.

[0064] Also, for the sake of improving the refractive index of theprimer film, metal oxide fine particles such as titanium oxide fineparticles can be contained in the primer layer.

[0065] Especially, by providing the primer layer in the polysulfidebond-containing plastic substrate having a refractive index of fromabout 1.68 to 1.76 and further providing the antireflection film of theinvention, it is possible to obtain an optical member having excellentimpact resistance, adhesiveness and resistance to scuffing even when thecenter thickness of the substrate is small.

[0066] With respect to the constitution of the primer layer and thecured layer in the optical member, it is preferable to provide theprimer layer and the cured layer in this order from the plasticsubstrate between the plastic substrate and the antireflection film.

EXAMPLES

[0067] The invention will be specifically described below with referenceto the following Examples, but it should not be construed that theinvention is limited thereto.

[0068] Incidentally, the physical properties of the optical membersobtained in the Examples and Comparative Examples were evaluated in thefollowing methods.

[0069] Evaluation of Physical Properties

[0070] (1) Luminous Transmittance:

[0071] With respect to a plastic lens having an antireflection film onthe both surfaces thereof as a sample, a luminous transmittance Y₁ ofthe plastic lens was measured using a Hitachi's spectrophotometerU-3410.

[0072] (2) Luminous Reflectance:

[0073] With respect to a plastic lens having an antireflection film onthe both surfaces thereof as a sample, a luminous reflectance Y₂ of theplastic lens was measured using a Hitachi's spectrophotometer U-3410.

[0074] (3) Impact Resistance:

[0075] A lens having a lens diopter 0.00D and having a lens centerthickness (hereinafter referred to as “CT”) of 1.0 mm or 2.0 mm wasprepared and subjected to drop ball test defined in FDA (Food and DrugAdministration), and the acceptance was expressed by “◯”, whereas therejection was expressed by “×”. Incidentally, the ball had a weight of14 g. Further, the drop ball test was continued until the lens had beenbroken, thereby confirming the strength as a maximum load.

[0076] (4) Adhesiveness:

[0077] One hundred cells of 1 mm×1 mm were prepared on the surface of aplastic lens using a cutter knife, a cellophane adhesive tape(manufactured by Nichiban Co., Ltd.) was stuck on the cells, and thetape was then peeled away at one stroke, thereby evaluating theadhesiveness in terms of the number of remaining cells. In the table,the number of remaining cells per 100 cells was designated.

[0078] (5) Abrasion Resistance:

[0079] The surface of a plastic lens was rubbed at 10 strokes by a steelwool (specification: #0000, manufactured by Nippon Steel Wool Co., Ltd.)while applying a load of 1 kgf/cm² and evaluated with respect to thesurface state according to the following criteria.

[0080] UA: Scuffs were not substantially present.

[0081] A: Several fine scuffs were present.

[0082] B: A number of fine scuffs and several thick scuffs were present

[0083] C: A number of fine scuffs and a number of thick scuffs werepresent.

[0084] D: The film was substantially stripped away.

[0085] (6) Heat Resistance:

[0086] A plastic lens was heated in a dry oven for one hour whileelevating the temperature at a rate of 5° C. from 60° C., therebymeasuring a temperature at which cracks were generated.

[0087] (7) Alkali Resistance:

[0088] A plastic lens was dipped in a 10% NaOH aqueous solution at 20°C. for one hour and evaluated with respect to the surface stateaccording to the following criteria.

[0089] UA: The plastic lens did not substantially change.

[0090] A: Spot-like film stripping was found in several portions.

[0091] B: Spot-like film stripping was entirely found.

[0092] C: Spot-like film stripping was entirely found, and planar filmstripping was found in several portions.

[0093] D: Film stripping was substantially entirely found.

[0094] (8) Measurement of Bayer Value:

[0095] A Bayer value was measured according to a difference in change ofthe haze value from a standard lens using an abrasion tester,BTE™@Abrasion Tester (manufactured by Colts Laboratories, USA) and ahaze value analyzer (manufactured by Murakami Color ResearchLaboratory). A Bayer value is the result of a standard test comparingthe haze value of a standard lens compared to the haze value of a testlens. A lens having a higher Bayer value has better abrasion resistance.For example, a value of 2.0 means that the test lens abraded two timesless than the standard lens.

[0096] Sample Number and Measurement Method

[0097] (1) Three standard lenses (CR39 substrates) and three samplelenses were prepared.

[0098] (2) The haze value before the abrasion test was measured.

[0099] (3) The abrasion properties were tested using a BTE™@AbrasionTester (600 reciprocations of surface abrasion by sand).

[0100] (4) The haze value after the abrasion test was measured.

[0101] (5) The Bayer value was calculated (an average value of threelenses). The Bayer value as referred to herein means [(change in hazevalue of standard lens)/(change in haze value of sample lens)].

[0102] Plastic Lens Substrate to be Used

[0103] (1) Substrate A: Diethylene glycol bisallyl carbonate having arefractive index of 1.50, a center thickness of 2.0 mm and a lensdiopter of 0.00.

[0104] (2) Substrate B: EYRY substrate (a trade name of Hoya Corporationhaving a polysulfide bond) having a refractive index of 1.71, a centerthickness of 1.0 mm and a lens diopter of 0.00.

[0105] Preparation of Coating Composition A

[0106] In a glass container, a liquid containing 90 parts by weight ofcolloidal silica (SNOWTEX-40 manufactured by Nissan Chemical Industries,Ltd.), 81.6 parts by weight of methyltrimethoxysilane as theorganosilicon compound, 176 parts by weight ofγ-glycidoxypropyltrimethoxysilane, 2.0 parts by weight of 0.5 Nhydrochloric acid, 20 parts by acetic acid, and 90 parts by weight ofwater was stirred at room temperature for 8 hours and then allowed tostand at room temperature for 16 hours to obtain a hydrolytic solution.To this solution, 120 parts by weight of isopropyl alcohol, 120 parts byweight of n-butyl alcohol, 16 parts by weight of aluminum acetylacetone,0.2 parts by weight of a silicone based surfactant, and 0.1 parts byweight of an ultraviolet ray absorber were added, and the mixture wasstirred at room temperature for 8 hours and then ripened at roomtemperature for 24 hours to obtain a coating liquid. A cured filmobtained from this coating composition is hereinafter sometimes referredto as “hard coat layer A”.

[0107] Preparation of Coating Composition B

[0108] In a glass container, 1,045 parts by weight ofγ-glycidoxypropyl(-trimethoxy)silane and 200 parts by weight ofγ-glycidoxypropyl-methyl(diethoxy)silane were charged, to which was thenadded 299 parts by weight of 0.01 moles/L hydrochloric acid whilestirring. Stirring was continued a whole day and night in a clean roomat 10° C. to obtain a silane hydrolyzate.

[0109] In another container, 4,018 parts by weight of methyl cellosolveand 830 parts by weight of isopropanol were added to 3,998 parts byweight of a composite fine particle sol composed mainly of titaniumoxide, zirconium oxide and silicon oxide (dispersed in methanol, totalsolids content: 30% by weight, mean particle size: from 5 to 8 μm) andstirred and mixed. Further, 4 parts by weight of a silicone basedsurfactant (“L-7001” manufactured by Nippon Unicar Co., Ltd.) and 100parts by weight of acetylacetonatoaluminum were added to the mixture.Stirring was continued a whole day and night in a clean room at 10° C.in the same manner as described previously. The reaction mixture wasmixed with the foregoing hydrolyzate, and the mixture was furtherstirred a whole day and night. Thereafter, the reaction mixture wasfiltered through a 3 μm-filter to obtain a hard coating liquid B. Acured film obtained from this coating composition is hereinaftersometimes referred to as “hard coat layer B”.

[0110] Formation of Cured Film

[0111] The plastic lens substrate A or B having been pre-treated with analkaline aqueous solution was dipped in the foregoing coating liquid andafter completion of dipping, lifted at a lifting rate of 20 cm/min. Theresulting plastic lens was heated at 120° C. for 2 hours to form a curedfilm (the hard coat layer A or heard coat layer B).

[0112] Ion Gun Treatment

[0113] The cured film was ion irradiated by an ion gun under theconditions of ion accelerating voltage, irradiation time and gasatmosphere as shown in the table.

[0114] Formation of Antireflection Film having Hybrid Film

[0115] An antireflection film comprising from first to seventh layerswas formed on the ion irradiated hard coat layer A or layer B under theconditions shown in Table 1, to obtain a plastic lens.

[0116] Incidentally, the hybrid layer was formed by binary vapordeposition of vapor deposition with an inorganic substance and vapordeposition with an organic substance using a device shown in FIG. 1while setting up the condition so as to carry out the vapor depositionsubstantially simultaneously. In the vapor deposition with an organicsubstance, the organic substance was vaporized in an external heatingtank and then introduced into the vapor deposition device using a gasvalve and a mass flow controller. In the formation of the hybrid layer,ion beam assisted deposition was employed in an atmosphere of a mixedgas of an argon gas and an oxygen gas. Also, the expression “−” in thetable means that the layer was formed by usual vacuum deposition withoutusing the ion beam assisted deposition. In the table, M1, CM1 and CM2stand for an inorganic substance, an organosilicon compound, and anorganic compound not containing silicon, respectively.

[0117] The details of the organic compounds described in the table areas follows.

[0118] (1) Epolite 70P (propylene glycol diglycidyl ether, molecularweight: about 188, manufactured by Kyoeisha Chemical Co., Ltd.)

[0119] (2) LS:1370 (diethoxydimethylsilane, molecular weight: 148.3,manufactured by Shin-Etsu Chemical Co., Ltd.)

[0120] (3) Epiol P200 (polypropylene glycol glycidyl ethen, averagemolecular weight: about 304, manufactured by NOF Corporation)

[0121] Incidentally, in Examples 5, 6, 9 and 10 and Comparative Examples3 and 4, a primer layer was provided between the substrate and the curedcoating film. The method of forming the primer layer is as follows.

[0122] Formation of primer layer

[0123] A mixture consisting of 6.65 parts by weight of a polyester typepolyol (Desmophene A-670, a trade name of Sumitomo Bayer Urethane Co.,Ltd.), 6.08 parts by weight of a block type polyisocyanate (BL-3175, atrade name of Sumitomo Bayer Urethane Co., Ltd.), 0.17 parts by weightof dibutyltin dilaurate as a curinh catalyst, 0.17 parts by weight of afluorine based leveling agent (Fluorad FC-430, a trade name of Sumitomo3M Limited) as a leveling agent, and 95.71 parts by weight of discetonealcohol as a solvent was thoroughly stirred until the mixture becameuniform. The resulting liquid primer was coated on the substrate lenshaving been pre-treated with an alkaline aqueous solution by dipping(lifting rate: 24 cm/min) and then heated for curing at 100° C. for 40minutes to form a primer layer having a thickness of from 2 to 3 μm.

Examples 1 and 10 and Comparative Examples 1 to 4

[0124] An antireflection film was provided on a substrate according tothe constitution shown in Tables 1-1 to 1-14, and physical propertieswere evaluated. The results are shown in Table 2. Incidentally, theexpression “λ” means a wavelength of light. TABLE 1-1 Constitution ofantireflection film Example 1 Plastic lens Substrate A substrate Hardcoat Layer A layer Ion gun for Accelerating voltage: 400 V, acceleratingcurrent: 170 mA pre- treatment Setting 60 sec (treatment time) conditionGas used Oxygen gas 10 sccm + Argon gas 10 sccm Substance used, filmSetting values thickness of ion gun First layer Film thickness: 0.438λAccelerating voltage: 200 V Refractive index: 1.468 Acceleratingcurrent: 120 mA M1: SiO₂ O₂: 10 sccm CM1: LS:1370 20 sccm Ar: 10 sccmCM2: Epiol P200 50 sccm Second layer Nb₂O₅: 0.0505λ — Third layer Filmthickness: 0.110λ Accelerating voltage: 200 V Refractive index: 1.468Accelerating current: 120 mA M1: SiO₂ O₂: 10 sccm CM1: LS:1370 20 sccmAr: 10 sccm CM2: Epiol P200 20 sccm Fourth layer Nb₂O₅: 0.1357λ — Fifthlayer Film thickness: 0.0689λ Accelerating voltage: 200 V Refractiveindex: 1.468 Accelerating current: 120 mA M1: SiO₂ O₂: 10 sccm CM1:LS:1370 20 sccm Ar: 10 sccm CM2: Epiol P200 20 sccm Sixth layer Nb₂O₅:0.1357λ — Seventh Film thickness: 0.271λ Accelerating voltage: 200 Vlayer Refractive index: 1.468 Accelerating current: 120 mA M1: SiO₂ O₂:10 sccm CM1: LS:1370 20 sccm Ar: 10 sccm CM2: Epiol P200 50 sccm

[0125] TABLE 1-2 Constitution of antireflection film Example 2 Plasticlens Substrate A substrate Hard coat Layer A layer Ion gun forAccelerating voltage: 400 V, accelerating current: 170 mA pre- treatmentSetting 60 sec (treatment time) condition Gas used Oxygen gas 10 sccm +Argon gas 10 sccm Substance used, film Setting values thickness of iongun First layer Film thickness: 0.488λ Accelerating voltage: 200 VRefractive index: 1.471 Accelerating current: 120 mA M1: SiO₂ + Al₂O₃O₂: 10 sccm CM1: LS:1370 20 sccm Ar: 10 sccm CM2: Epiol P200 50 sccmSecond layer Nb₂O₅: 0.055λ — Third layer Film thickness: 0.115λAccelerating voltage: 200 V Refractive index: 1.471 Acceleratingcurrent: 120 mA M1: SiO₂ + Al₂O₃ O₂: 10 sccm CM1: LS:1370 20 sccm Ar: 10sccm CM2: Epiol P200 20 sccm Fourth layer Nb₂O₅: 0.1427λ — Fifth layerFilm thickness: 0.0740λ Accelerating voltage: 200 V Refractive index:1.471 Accelerating current: 120 mA M1: SiO₂ + Al₂O₃ O₂: 10 sccm CM1:LS:1370 20 sccm Ar: 10 sccm CM2: Epiol P200 20 sccm Sixth layer Nb₂O₅:0.128λ — Seventh Film thickness: 0.275λ Accelerating voltage: 200 Vlayer Refractive index: 1.471 Accelerating current: 120 mA M1: SiO₂ +Al₂O₃ O₂: 10 sccm CM1: LS:1370 20 sccm Ar: 10 sccm CM2: Epiol P200 50sccm

[0126] TABLE 1-3 Constitution of antireflection film Example 3 Plasticlens Substrate A substrate Hard coat Layer A layer Ion gun forAccelerating voltage: 400 V, Accelerating current: 170 mA pre- treatmentSetting 60 sec (treatment time) condition Gas used Oxygen gas 10 sccm +Argon gas 10 sccm Substance used, film Setting values thickness of iongun First layer Film thickness: 0.438λ Accelerating voltage: 200 VRefractive index: 1.468 Accelerating current: 120 mA M1: SiO₂ O₂: 10sccm CM1: LS:1370 20 sccm Ar: 10 sccm CM2: Epiol P200 20 sccm Secondlayer Film thickness: 0.035λ Accelerating voltage: 200 V Refractiveindex: 2.13 Accelerating current: 120 mA M1: Nb₂O₅ O₂: 20 sccm CM1:LS:1370 5 sccm CM2: Epiol P200 5 sccm Third layer Film thickness: 0.110λAccelerating voltage: 200 V Refractive index: 1.468 Acceleratingcurrent: 120 mA M1: SiO₂ O₂: 10 sccm CM1: LS:1370 20 sccm Ar: 10 sccmCM2: Epiol P200 20 sccm Fourth layer Film thickness: 0.1320λAccelerating voltage: 200 V Refractive index: 2.13 Accelerating current:120 mA M1: Nb₂O₅ O₂: 20 sccm CM1: LS:1370 5 sccm CM2: Epiol P200 5 sccmFifth layer Film thickness: 0.0689λ Accelerating voltage: 200 VRefractive index: 1.468 Accelerating current: 120 mA M1: SiO₂ O₂: 10sccm CM1: LS:1370 20 sccm Ar: 10 sccm CM2: Epiol P200 20 sccm Sixthlayer Film thickness: 0.1220λ Accelerating voltage: 200 V Refractiveindex: 2.13 Accelerating current: 120 mA M1: Nb₂O₅ O₂: 20 sccm CM1:LS:1370 5 sccm CM2: Epiol P200 5 sccm Seventh Film thickness: 0.271λAccelerating voltage: 200 V layer Refractive index: 1.468 Acceleratingcurrent: 120 mA M1: SiO₂ O₂: 10 sccm CM1: LS:1370 20 sccm Ar: 10 sccmCM2: Epiol P200 50 sccm

[0127] TABLE 1-4 Constitution of antireflection film Example 4 Plasticlens Substrate A substrate Hard coat Layer A layer Ion gun forAccelerating voltage: 400 V, accelerating current: 170 mA pre- treatmentSetting 60 sec (treatment time) condition Gas used Oxygen gas 10 sccm +Argon gas 10 sccm Substance used, film Setting values thickness of iongun First layer Film thickness: 0.488λ Accelerating voltage: 200 VRefractive index: 1.471 Accelerating current: 120 mA M1: SiO₂ + Al₂O₃O₂: 10 sccm CM1: LS:1370 20 sccm Ar: 10 sccm CM2: Epiol P200 20 sccmSecond layer Film thickness: 0.035λ Accelerating voltage: 200 VRefractive index: 2.13 Accelerating current: 120 mA M1: Nb₂O₅ O₂: 20sccm CM1: LS:1370 5 sccm CM2: Epiol P200 5 sccm Third layer Filmthickness: 0.115λ Accelerating voltage: 200 V Refractive index: 1.471Accelerating current: 120 mA M1: SiO₂ + Al₂O₃ O₂: 10 sccm CM1: LS:137020 sccm Ar: 10 sccm CM2: Epiol P200 20 sccm Fourth layer Film thickness:0.1421λ Accelerating voltage: 200 V Refractive index: 2.13 Acceleratingcurrent: 120 mA M1: Nb₂O₅ O₂: 20 sccm CM1: LS:1370 5 sccm CM2: EpiolP200 5 sccm Fifth layer Film thickness: 0.0740λ Accelerating voltage:200 V Refractive index: 1.471 Accelerating current: 120 mA M1: SiO₂ +Al₂O₃ O₂: 10 sccm CM1: LS:1370 20 sccm Ar: 10 sccm CM2: Epiol P200 20sccm Sixth layer Film thickness: 0.1184λ Accelerating voltage: 200 VRefractive index: 2.13 Accelerating current: 120 mA M1: Nb₂O₅ O₂: 20sccm CM1: LS:1370 5 sccm CM2: Epiol P200 5 sccm Seventh Film thickness:0.275λ Accelerating voltage: 200 V layer Refractive index: 1.471Accelerating current: 120 mA M1: SiO₂ + Al₂O₃ O₂: 10 sccm CM1: LS:137020 sccm Ar: 10 sccm CM2: Epiol P200 50 sccm

[0128] TABLE 1-5 Constitution of antireflection film Example 5 Plasticlens Substrate B substrate Hard coat Layer B (A primer layer is presentbetween the lens layer substrate and the layer B) Ion gun forAccelerating voltage: 400 V, accelerating current: 170 mA pre- treatmentSetting 60 sec (treatment time) condition Gas used Oxygen gas 10 sccm +Argon gas 10 sccm Substance used, film Setting values thickness of iongun First layer Film thickness: 0.0534λ Accelerating voltage: 200 VRefractive index: 1.468 Accelerating current: 120 mA M1: SiO₂ O₂: 10sccm CM2: Epolite 70P 20 sccm Ar: 10 sccm Second layer Nb₂O₅: 0.0319λAccelerating voltage: 450 V Accelerating current: 180 mA O₂: 20 sccmThird layer Film thickness: 0.5452λ Accelerating voltage: 200 VRefractive index: 1.468 Accelerating current: 120 mA M1: SiO₂ O₂: 10sccm CM2: Epolite 70P 20 sccm Ar: 10 sccm Fourth layer Nb₂O₅: 0.1001λAccelerating voltage: 450 V Accelerating current: 180 mA O₂: 20 sccmFifth layer Film thickness: 0.1094λ Accelerating voltage: 200 VRefractive index: 1.468 Accelerating current: 120 mA M1: SiO₂ O₂: 10sccm CM2: Epolite 70P 20 sccm Ar: 10 sccm Sixth layer Nb₂O₅: 0.1497λAccelerating voltage: 450 V Accelerating current: 180 mA O₂: 20 sccmSeventh Film thickness: 0.2892λ Accelerating voltage: 200 V layerRefractive index: 1.468 Accelerating current: 120 mA M1: SiO₂ O₂: 10sccm CM2: Epolite 70P 20 sccm Ar: 10 sccm

[0129] TABLE 1-6 Constitution of antireflection film Example 6 Plasticlens Substrate B substrate Hard coat Layer B (A primer layer is presentbetween the lens layer substrate and the layer B) Ion gun forAccelerating voltage: 400 V, accelerating current: 170 mA pre- treatmentSetting 60 sec (treatment time) condition Gas used Oxygen gas 10 sccm +Argon gas 10 sccm Substance used, film Setting values thickness of iongun First layer Film thickness: 0.0534λ Accelerating voltage: 200 VRefractive index: 1.471 Accelerating current: 120 mA M1: SiO₂ + Al₂O₃O₂: 10 sccm CM2: Epolite 70P 20 sccm Ar: 10 sccm Second layer Nb₂O₅:0.0319λ Accelerating voltage: 450 V Accelerating current: 180 mA O₂: 20sccm Third layer Film thickness: 0.5680λ Accelerating voltage: 100 VRefractive index: 1.471 Accelerating current: 70 mA M1: SiO₂ + Al₂O₃ O₂:10 sccm CM2: Epolite 70P 20 sccm Ar: 10 sccm Fourth layer Nb₂O₅: 0.0908λAccelerating voltage: 450 V Accelerating current: 180 mA O₂: 20 sccmFifth layer Film thickness: 0.0992λ Accelerating voltage: 200 VRefractive index: 1.471 Accelerating current: 120 mA M1: SiO₂ + Al₂O₃O₂: 10 sccm CM2: Epolite 70P 20 sccm Ar: 10 sccm Sixth layer Nb₂O₅:0.158λ Accelerating voltage: 450 V Accelerating current: 180 mA O₂: 20sccm Seventh Film thickness: 0.2902λ Accelerating voltage: 200 V layerRefractive index: 1.471 Accelerating current: 120 mA M1: SiO₂ + Al₂O₃O₂: 10 sccm CM2: Epolite 70P 20 sccm Ar: 10 sccm

[0130] TABLE 1-7 Constitution of antireflection film Example 7 Plasticlens Substrate A substrate Hard coat Layer A layer Ion gun forAccelerating voltage: 400 V, accelerating current: 170 mA pre- treatmentSetting 60 sec (treatment time) condition Gas used Oxygen gas 10 sccm +Argon gas 10 sccm Substance used, film Setting values thickness of iongun First layer Film thickness: 0.0534λ Accelerating voltage: 200 VRefractive index: 1.468 Accelerating current: 120 mA M1: SiO₂ O₂: 10sccm CM2: Epolite 70P 20 sccm Ar: 10 sccm Second layer Nb₂O₅: 0.0319λAccelerating voltage: 450 V Accelerating current: 180 mA O₂: 20 sccmThird layer Film thickness: 0.5452λ Accelerating voltage: 200 VRefractive index: 1.468 Accelerating current: 120 mA M1: SiO₂ O₂: 10sccm CM2: Epolite 70P 20 sccm Ar: 10 sccm Fourth layer Nb₂O₅: 0.1001λAccelerating voltage: 450 V Accelerating current: 180 mA O₂: 20 sccmFifth layer Film thickness: 0.1094λ Accelerating voltage: 200 VRefractive index: 1.468 Accelerating current: 120 mA M1: SiO₂ O₂: 10sccm CM2: Epolite 70P 20 sccm Ar: 10 sccm Sixth layer Nb₂O₅: 0.1497λAccelerating voltage: 450 V Accelerating current: 180 mA O₂: 20 sccmSeventh Film thickness: 0.2892λ Accelerating voltage: 200 V layerRefractive index: 1.468 Accelerating current: 120 mA M1: SiO₂ O₂: 10sccm CM2: Epolite 70P 20 sccm Ar: 10 sccm

[0131] TABLE 1-8 Constitution of antireflection film Example 8 Plasticlens Substrate A substrate Hard coat Layer A layer Ion gun forAccelerating voltage: 400 V, accelerating current: 170 mA pre- treatmentSetting 60 sec (treatment time) condition Gas used Oxygen gas 10 sccm +Argon gas 10 sccm Substance used, film Setting values thickness of iongun First layer Film thickness: 0.0534λ Accelerating voltage: 200 VRefractive index: 1.471 Accelerating current: 120 mA M1: SiO₂ + Al₂O₃O₂: 10 sccm CM2: Epolite 70P 20 sccm Ar: 10 sccm Second layer Nb₂O₅:0.0319λ Accelerating voltage: 450 V Accelerating current: 180 mA O₂: 20sccm Third layer Film thickness: 0.5680λ Accelerating voltage: 100 VRefractive index: 1.471 Accelerating current: 70 mA M1: SiO₂ + Al₂O₃ O₂:10 sccm CM2: Epolite 70P 20 sccm Ar: 10 sccm Fourth layer Nb₂O₅: 0.0908λAccelerating voltage: 450 V Accelerating current: 180 mA O₂: 20 sccmFifth layer Film thickness: 0.0992λ Accelerating voltage: 200 VRefractive index: 1.471 Accelerating current: 120 mA M1: SiO₂ + Al₂O₃O₂: 10 sccm CM2: Epolite 70P 20 sccm Ar: 10 sccm Sixth layer Nb₂O₅:0.158λ Accelerating voltage: 450 V Accelerating current: 180 mA O₂: 20sccm Seventh Film thickness: 0.2902λ Accelerating voltage: 200 V layerRefractive index: 1.471 Accelerating current: 120 mA M1: SiO₂ + Al₂O₃O₂: 10 sccm CM2: Epolite 70P 20 sccm Ar: 10 sccm

[0132] TABLE 1-9 Constitution of antireflection film Example 9 Plasticlens Substrate B substrate Hard coat Layer B (A primer layer is presentbetween the lens layer substrate and the layer B) Ion gun forAccelerating voltage: 400 V, accelerating current: 170 mA pre- treatmentSetting 60 sec (treatment time) condition Gas used Oxygen gas 10 sccm +Argon gas 10 sccm Substance used, film Setting values thickness of iongun First layer Film thickness: 0.0534λ Accelerating voltage: 200 VRefractive index: 1.468 Accelerating current: 120 mA M1: SiO₂ O₂: 10sccm CM2: Epolite 70P 20 sccm Ar: 10 sccm Second layer Nb₂O₅: 0.0319λAccelerating voltage: 450 V Refractive index: 2.21 Accelerating current:180 mA CM2: Epolite 70P 5 sccm O₂: 20 sccm Third layer Film thickness:0.561λ Accelerating voltage: 200 V Refractive index: 1.468 Acceleratingcurrent: 120 mA M1: SiO₂ O₂: 10 sccm CM2: Epolite 70P 20 sccm Ar: 10sccm Fourth layer Nb₂O₅: 0.1001λ Accelerating voltage: 450 V Refractiveindex: 2.21 Accelerating current: 180 mA CM2: Epolite 70P 5 sccm O₂: 20sccm Fifth layer Film thickness: 0.0974λ Accelerating voltage: 200 VRefractive index: 1.468 Accelerating current: 120 mA M1: SiO₂ O₂: 10sccm CM2: Epolite 70P 20 sccm Ar: 10 sccm Sixth layer Nb₂O₅: 0.1497λAccelerating voltage: 450 V Refractive index: 2.21 Accelerating current:180 mA CM2: Epolite 70P 20 sccm O₂: 20 sccm Seventh Film thickness:0.2892λ Accelerating voltage: 200 V layer Refractive index: 1.468Accelerating current: 120 mA M1: SiO₂ O₂: 10 sccm CM2: Epolite 70P 20sccm Ar: 10 sccm

[0133] TABLE 1-10 Constitution of antireflection film Example 10 Plasticlens Substrate B substrate Hard coat Layer B (A primer layer is presentbetween the lens layer substrate and the layer B) Ion gun forAccelerating voltage: 400 V, accelerating current: 170 mA pre- treatmentSetting 60 sec (treatment time) condition Gas used Oxygen gas 10 sccm +Argon gas 10 sccm Substance used, film Setting values thickness of iongun First layer Film thickness: 0.0534λ Accelerating voltage: 200 VRefractive index: 1.471 Accelerating current: 120 mA M1: SiO₂ + Al₂O₃O₂: 10 sccm CM2: Epolite 70P 20 sccm Ar: 10 sccm Second layer Nb₂O₅:0.0319λ Accelerating voltage: 450 V Refractive index: 2.21 Acceleratingcurrent: 180 mA CM2: Epolite 70P 5 sccm O₂: 20 sccm Third layer Filmthickness: 0.575λ Accelerating voltage: 200 V Refractive index: 1.471Accelerating current: 120 mA M1: SiO₂ + Al₂O₃ O₂: 10 sccm CM2: Epolite70P 20 sccm Ar: 10 sccm Fourth layer Nb₂O₅: 0.0908λ Acceleratingvoltage: 450 V Refractive index: 2.21 Accelerating current: 180 mA CM2:Epolite 70P 5 sccm O₂: 20 sccm Fifth layer Film thickness: 0.0952λAccelerating voltage: 200 V Refractive index: 1.471 Acceleratingcurrent: 120 mA M1: SiO₂ + Al₂O₃ O₂: 10 sccm CM2: Epolite 70P 20 sccmAr: 10 sccm Sixth layer Nb₂O₅: 0.158λ Accelerating voltage: 450 VRefractive index: 2.21 Accelerating current: 180 mA CM2: Epolite 70P 5sccm O₂: 20 sccm Seventh Film thickness: 0.2902λ Accelerating voltage:200 V layer Refractive index: 1.471 Accelerating current: 120 mA M1:SiO₂ + Al₂O₃ O₂: 10 sccm CM2: Epolite 70P 20 sccm Ar: 10 sccm

[0134] TABLE 1-11 Comparative antireflection film Comparative Example 1Plastic Substrate A lens substrate Hard coat layer Layer A Ion gun forpre- Accelerating voltage: 400 V, treatment accelerating current: 170 mASetting condition 60 sec (treatment time) Gas used Oxygen gas 10 sccm +Argon gas 10 sccm Substance used, film Setting values thickness of iongun First layer Film thickness: 0.438λ — Refractive index: 1.471 M1:SiO₂ Second layer Nb₂O₅: 0.0505λ — Third layer Film thickness: 0.110λ —Refractive index: 1.471 M1: SiO₂ Fourth layer Nb₂O₅: 0.1357λ — Fifthlayer Film thickness: 0.0689λ — Refractive index: 1.471 M1: SiO₂ Sixthlayer Nb₂O₅: 0.1357λ — Seventh layer Film thickness: 0.271λ — Refractiveindex: 1.471 M1: SiO₂

[0135] TABLE 1-12 Comparative antireflection film Comparative Example 2Plastic Substrate A lens substrate Hard coat layer Layer A Ion gunAccelerating voltage: 400 V, for pre- accelerating current: 170 mAtreatment Setting 60 sec (treatment time) condition Gas used Oxygen gas10 sccm + Argon gas 10 sccm Substance used, film Setting valuesthickness of ion gun First layer Film thickness: 0.511λ Acceleratingvoltage: 200 V Refractive index: 1.468 Accelerating current: 120 mA M1:SiO₂ O₂: 10 sccm Ar: 10 sccm Second layer Nb₂O₅: 0.055λ — Third layerFilm thickness: 0.115λ Accelerating voltage: 200 V Refractive index:1.468 Accelerating current: 120 mA M1: SiO₂ O₂: 10 sccm Ar: 10 sccmFourth layer Nb₂O₅: 0.1427λ — Fifth layer Film thickness: 0.0740λAccelerating voltage: 200 V Refractive index: 1.468 Acceleratingcurrent: 120 mA M1: SiO₂ O₂: 10 sccm Ar: 10 sccm Sixth layer Nb₂O₅:0.128λ — Seventh layer Film thickness: 0.275λ Accelerating voltage: 200V Refractive index: 1.468 Accelerating current: 120 mA M1: SiO₂ O₂: 10sccm Ar: 10 sccm

[0136] TABLE 1-13 Comparative antireflection film Comparative Example 3Plastic Substrate B lens substrate Hard coat layer Layer B (A primerlayer is present between the lens substrate and the layer B) Ion gun forpre- Accelerating voltage: 400 V, treatment accelerating current: 170 mASetting condition 60 sec (treatment time) Gas used Oxygen gas 10 sccm +Argon gas 10 sccm Substance used, film Setting values thickness of iongun First layer Film thickness: 0.0539λ — Refractive index: 1.471 M1:SiO₂ Second layer Nb₂O₅: 0.0325λ — Third layer Film thickness: 0.560λ —Refractive index: 1.471 M1: SiO₂ Fourth layer Nb₂O₅: 0.107λ — Fifthlayer Film thickness: 0.115λ — Refractive index: 1.471 M1: SiO₂ Sixthlayer Nb₂O₅: 0.1394λ — Seventh layer Film thickness: 0.289λ — Refractiveindex: 1.471 M1: SiO₂

[0137] TABLE 1-14 Comparative antireflection film Comparative Example 4Plastic Substrate B lens substrate Hard coat layer Layer B (A primerlayer is present between the lens substrate and the layer B) Ion gunAccelerating voltage: 400 V, for pre- accelerating current: 170 mAtreatment Setting 60 sec (treatment time) condition Gas used Oxygen gas10 sccm + Argon gas 10 sccm Substance used, film Setting valuesthickness of ion gun First layer Film thickness: 0.0539λ Acceleratingvoltage: 200 V Refractive index: 1.468 Accelerating current: 120 mA M1:SiO₂ O₂: 10 sccm Ar: 10 sccm Second layer Nb₂O₅: 0.0325λ — Third layerFilm thickness: 0.572λ Accelerating voltage: 200 V Refractive index:1.468 Accelerating current: 120 mA M1: SiO₂ O₂: 10 sccm Ar: 10 sccmFourth layer Nb₂O₅: 0.1025λ — Fifth layer Film thickness: 0.108λAccelerating voltage: 200 V Refractive index: 1.468 Acceleratingcurrent: 120 mA M1: SiO₂ O₂: 10 sccm Ar: 10 sccm Sixth layer Nb₂O₅:0.1402λ — Seventh layer Film thickness: 0.291λ Accelerating voltage: 200V Refractive index: 1.468 Accelerating current: 120 mA M1: SiO₂ O₂: 10sccm Ar: 10 sccm

[0138] TABLE 2 Evaluation of film performance LR²⁾ LT³⁾ Abrasion HeatAlkali Bayer Example¹⁾ Y₁ % Y₂ % Impact resistance Adhesivenessresistance resistance resistance value E-1 0.82% 99.0% CT = 2.0, FDA: O,100/100 UA  95° C. UA 10.0  28 g at max. E-2 0.82% 99.0% CT = 2.0, FDA:O, 100/100 UA  95° C. UA 10.0  28 g at max. E-3 0.82% 99.0% CT = 2.0,FDA: O, 100/100 UA  95° C. UA 11.0  36 g at max. E-4 0.82% 99.0% CT =2.0, FDA: O, 100/100 UA  95° C. UA 11.0 368 g at max. E-5 0.82% 99.0% CT= 1.0, FDA: O, 100/100 UA 100° C. UA 12.0 100 g at maximum E-6 0.82%99.0% CT = 1.0, FDA: O, 100/100 UA 100° C. UA 12.0 100 g at maximum E-70.82% 99.0% CT = 2.0, FDA: O, 100/100 UA  95° C. UA 12.5  36 g E-8 0.82%99.0% CT = 2.0, FDA: O, 100/100 UA  95° C. UA 12.5  36 g E-9 0.82% 99.0%CT = 1.0, FDA: O, 100/100 UA 105° C. UA 12.0 100 g E-10 0.82% 99.0% CT =1.0, FDA: O, 100/100 UA 105° C. UA 12.0 100 g CE-1  1.0% 98.8% CT = 2.0,FDA: X 100/100 UA  70° C. UA 3.0 CE-2 0.82% 99.0% CT = 2.0, FDA: X100/100 UA  80° C. UA 5.5 CE-3  1.0% 98.8% CT = 1.0, FDA: O, 100/100 UA 80° C. UA 2.7 100 g CE-4  1.0% 98.8% CT = 1.0, FDA: O, 100/100 UA to A 85° C. UA 3.5 100 g

[0139] The results of Examples 1-4, 7 and 8 are to be compared withthose of Comparative Examples 1 and 2, and the results of Examples 5, 6,9 and 10 are to be compared with those of Comparative Examples 3 and 4.In comparison with the results of Comparative Examples 1 and 2, those ofExamples 1-4, 7 and 8 reveal that the impact resistance was good. Also,in comparison with the results of Comparative Examples 3 and 4, those ofExamples 5, 6, 9 and 10 reveal that the Bayer value was good.

[0140] The optical member of the invention not only has anantireflection film having excellent properties such as low reflectanceand high transmittance but also has excellent impact resistance,adhesiveness, heat resistance, abrasion resistance and alkali resistanceon the plastic substrate and is good in productivity.

[0141] While the invention has been described in connection with certainembodiments so that aspects thereof may be more fully understood andappreciated, it is not intended to limit the invention to theseparticular embodiments. On the contrary, it is intended to cover allalternatives, modifications and equivalents as may be included withinthe scope of the invention as defined by the appended claims.

What is claimed is:
 1. Optical member comprising a plastic substrate anda multilayered antireflection film formed by vapor deposition, whereinat least one layer in the antireflection film is a hybrid layer formedof the following materials as vapor deposition raw materials: (i) atleast one inorganic substance selected from silicon dioxide, aluminumoxide, titanium oxide, zirconium oxide, tantalum oxide, yttrium oxide,and niobium oxide, and (ii) at least one compound that is a liquid atnormal temperature and at atmospheric pressure selected from (ii-a) anorganosilicon compound and (ii-b) an organic compound not containingsilicon
 2. Optical member of claim 1, wherein the hybrid layer is formedby simultaneously vapor depositing the materials (i) and (ii) withseparate vapor deposition sources.
 3. Optical member of claim 2, whereinthe material (i) is vaporized by heating using an electron gun, and thematerial (ii) is stored in a tank and is vaporized by heating within thetank.
 4. Optical member of claim 1, wherein the hybrid layer is formedby ion beam assisted deposition.
 5. Optical member of claim 1, whereinthe material (ii) is vapor deposited by heating without adding asolvent.
 6. Optical member of claim 1, wherein the organosiliconcompound (ii-a) has a number average molecular weight of 48-320. 7.Optical member of claim 1, wherein the organic compound not containingsilicon (ii-b) has a number average molecular weight of 28-320. 8.Optical member of any of claims 1-4 and 6, wherein the organosiliconcompound (ii-a) is a compound of any of the general formulae (a)-(d):

wherein, m and n each independently represents an integer of 0 or more;and X₁-X₈ each independently represent H, a saturated or unsaturatedC₁₋₆-hydrocarbon group, —OR¹, —CH₂OR², —COOR³, —OCOR⁴, —SR⁵, —CH₂SR⁶,—NR⁷ ₂, or —CH₂NR⁸ ₂; wherein R¹ to R⁸ each independently represents Hor a saturated or unsaturated C₁₋₆-hydrocarbon group.
 9. Optical memberof any of claims 1-4 and 7, wherein the compound (ii-b) is a compound ofany of the general formulae (e)-(g):

wherein R⁹ is a C₁₋₁₀-hydrocarbon group, which may contain nitrogen oroxygen, R¹⁰ is a divalent C₁₋₇-hydrocarbon group, which may containoxygen, and X₉-X₁₂ each represents H, a C₁₋₁₀-hydrocarbon group, or anorganic group having 1-10 carbon atoms and containing C, H and at leastone of O and N as an essential component.
 10. Optical member of claim 8,wherein the content of the material (ii) in the hybrid layer is 0.02-25wt.-%.
 11. Optical member of claim 9, wherein the content of thematerial (ii) in the hybrid layer is 0.02-25 wt.-%.
 12. Optical memberof claim 1, wherein an undercoat layer made of at least one selectedfrom Ni, Ag, Pt, Nb and Ti and having a thickness of 1-5 nm is providedbetween the plastic substrate and the antireflection film.
 13. Opticalmember of claim 11, wherein the plastic substrate comprises diethyleneglycol bisallyl carbonate as a raw material.
 14. Optical member of claim1, wherein the plastic substrate comprises a polymer formed bypolymerizing a compound containing an epithio group.
 15. Optical memberof claim 1, wherein between the plastic substrate and the antireflectionfilm a primer layer and a cured layer are provided in this order fromthe plastic substrate.